施用组配固化剂对盆栽土壤重金属交换态含量及在水稻中累积分布的影响

通过盆栽试验,研究组配固化剂石灰石+海泡石在不同施用量(0、1.0、2.0、4.0、8.0、16.0 g·kg-1)下,盆栽土壤中重金属Pb、Cd、Zn交换态含量的变化与在水稻根、茎、壳和糙米的累积分布.结果表明:①土壤中Pb、Cd和Zn交换态含量随着组配固化剂施用量的增加呈明显降低趋势,交换态含量较对照分别降低了15.3%~99.9%、9.2%~99.9%和7.0%~99.9%,有效缓解了水稻对土壤Pb、Cd和Zn的吸收.②水稻生长状况得到改善,株高随组配固化剂施用量的增加逐渐上升.施用量在1.0 g·kg-1时,谷粒产量最大,与对照相比,增产60.4%.水稻各器官对Pb、Cd、Zn的吸收随施用量的增加逐渐下降;与对照相比,施用1.0~16.0 g·kg-1的组配固化剂后糙米中Pb、Cd和Zn含量下降幅度分别为2.2%~13.1%、29.3%~79.3%和19.5%~43.3%.     

组配改良剂对污染稻田中Pb、Cd、Cu和Zn钝化效果持续性比较

为研究组配改良剂碳酸钙+海泡石(LS)对稻田土壤重金属Pb、Cd、Cu、Zn钝化效果的持久性,通过一次性施用0、2、4、8 g·kg-1的LS,并分别于2012年(第一季)、2013年(第二季)和2014年(第三季)连续种植水稻,在湘南某矿区附近污染稻田进行了一个3 a的大田修复试验.结果表明:1LS能显著提高三季土壤p H值,且LS对土壤p H值提高效果为:第一季第二季第三季.2LS能显著降低三季水稻土壤中Pb、Cd、Zn的交换态含量,且第三季水稻土壤中Pb、Cd、Zn的交换态含量分别降低32.6%~97.7%、8.3%~71.4%和10.9%~83.5%,但对降低三季土壤中Cu的交换态含量无显著影响;LS降低三季土壤中Pb、Cd、Cu、Zn交换态含量的效果均为:PbZnCdCu.3LS使第三季水稻糙米中Pb和Cd含量分别降低26.7%~66.7%、59.1%~80.3%,这种降低效果均随着改良剂LS添加量的增加而增大,但对糙米中Cu和Zn含量无明显影响.LS降低糙米中Pb、Cd、Cu、Zn含量的效果为:第一季,PbCdCuZn;第二季,PbCdCuZn;第三季,CdPbZnCu.LS降低三季水稻糙米中重金属含量的整体效果为PbCdCuZn.4随着时间的延长,LS对土壤中Pb和Cd具有更稳定的钝化效果.因此,LS对治理Pb和Cd污染的土壤具有良好的持久性.     

2种组配改良剂对稻田土壤重金属有效性的效果

为研究2种组配改良剂LS(碳酸钙+海泡石)和HZ(羟基磷灰石+沸石)对土壤重金属的生物有效性以及水稻吸收累积重金属的影响,在湘南某矿区附近污染稻田中施用了不同添加量(0,2,4,8g/kg)的两种组配改良剂,并进行了水稻种植的田间试验.结果表明,施用2~8g/kg组配改良剂LS和HZ均能使土壤pH值和CEC含量显著增加,有机质含量变化不明显,LS比HZ更能提高土壤pH值和CEC含量.施用2~8g/kg组配改良剂LS能使土壤中Pb、Cd、Cu和Zn的TCLP提取态含量分别降低25.7%~52.2%、12.7%~25.7%、6.4%~17.2%和8.6%~23.4%,施用2~8g/kg HZ使土壤中Pb、Cd、Cu和Zn的TCLP提取态含量分别降低57.6%~80.1%、7.0%~40.9%、2.3%~22.7%和4.5%~33.2%.两种组配改良剂能显著降低土壤中Pb、Cd、Cu和Zn的生物有效性,抑制水稻植株对Pb和Cd的吸收,土壤Pb、Cd和Cu的TCLP提取态含量与水稻根系和糙米中Pb、Cd和Cu的含量之间存在显著或极显著的正相关关系,TCLP提取态含量能较好的表示重金属在土壤中的生物有效性.     

2种组配改良剂对稻田土壤重金属有效性的效果

为研究2种组配改良剂LS(碳酸钙+海泡石)和HZ(羟基磷灰石+沸石)对土壤重金属的生物有效性以及水稻吸收累积重金属的影响,在湘南某矿区附近污染稻田中施用了不同添加量(0,2,4,8g/kg)的两种组配改良剂,并进行了水稻种植的田间试验.结果表明,施用2~8g/kg组配改良剂LS和HZ均能使土壤pH值和CEC含量显著增加,有机质含量变化不明显,LS比HZ更能提高土壤pH值和CEC含量.施用2~8g/kg组配改良剂LS能使土壤中Pb、Cd、Cu和Zn的TCLP提取态含量分别降低25.7%~52.2%、12.7%~25.7%、6.4%~17.2%和8.6%~23.4%,施用2~8g/kg HZ使土壤中Pb、Cd、Cu和Zn的TCLP提取态含量分别降低57.6%~80.1%、7.0%~40.9%、2.3%~22.7%和4.5%~33.2%.两种组配改良剂能显著降低土壤中Pb、Cd、Cu和Zn的生物有效性,抑制水稻植株对Pb和Cd的吸收,土壤Pb、Cd和Cu的TCLP提取态含量与水稻根系和糙米中Pb、Cd和Cu的含量之间存在显著或极显著的正相关关系,TCLP提取态含量能较好的表示重金属在土壤中的生物有效性.     

外源锌刺激下水稻对土壤镉的累积效应

采用水稻盆栽实验研究不同含量外源Zn对模拟Cd中度污染和重度污染土壤中水稻低累积品种湘晚籼12和高累积品种威优46水稻各部位累积Cd的影响.结果表明,在Cd中度污染水平,外源Zn分别增大2种水稻各部位Cd含量,湘晚籼12和威优46糙米Cd含量分别增加125.0%~275.0%和6.6%~91.2%,但各处理糙米Cd含量不高于0.2 mg·kg~(-1);在Cd重度污染水平,外源Zn有降低水稻各部位中Cd含量的作用,湘晚籼12和威优46糙米Cd含量相应降低了16.6%~63.5%和15.6%~74.4%,且威优46糙米Cd含量随外源Zn施用含量的增大而逐渐降低,使得糙米中Cd含量低于0.2 mg·kg~(-1).水稻糙米累积Cd含量与土壤中Cd、Zn交换态含量的相关关系,因Cd污染程度和水稻品种的不同而不同.在Cd中度污染水平,湘晚籼12水稻糙米Cd含量与土壤中交换态Zn含量正线性相关,而威优46水稻糙米Cd含量与土壤中交换态Cd和Zn含量正线性相关;在Cd重度污染水平,威优46水稻糙米Cd含量与土壤中交换态Cd和Zn含量为负线性相关.在不造成土壤Zn污染的前提下,可向Cd重度污染土壤施用一定量的Zn肥,以降低糙米Cd含量,提高糙米品质.     

组配改良剂对污染稻田中铅、镉和砷生物有效性的影响

选取湖南某矿区重金属和砷复合污染稻田土,以盆栽实验研究了施用组配改良剂LMF(碳酸钙+偏高岭土+钙镁磷肥)对土壤中Pb、Cd和As的生物有效性和水稻糙米中Pb、Cd和As累积效应的影响.结果表明:施用LMF能显著增加供试土壤pH值、交换性盐基总量(TEB)和阳离子交换量(CEC),对盐基饱和度(BS)和有机质(OM)含量无显著影响.施用LMF能显著降低土壤中Pb、Cd的交换态和酸可提取态含量,以及降低Pb的TCLP提取态含量,对Cd的TCLP提取态含量无明显效果.LMF施用使土壤中As的交换态和TCLP提取态含量呈现先下降后上升的趋势,且均在施用量为2 g·kg-1时含量最低.随着LMF施用量的增加,水稻糙米中Pb、Cd的含量分别降低了8.44%~99.6%、27.5%~74.1%,而水稻糙米中As含量呈现出先下降后上升的趋势.除Cd的TCLP提取态和酸可提取态外,Pb、Cd和As的其它提取态含量与其在水稻糙米中的含量均呈现出显著正相关关系(p0.05或p0.01).     

长期不同耕作方式对紫色水稻土重金属含量及有效性的影响

通过长期定位试验,研究了常规平作、水旱轮作、免耕冬水、垄作免耕和厢作免耕5种耕作方式对紫色水稻土剖面重金属(Fe、Mn、Cu、Zn、Pb、Cd)总量、有效量及水稻根、茎叶和糙米重金属含量的影响.结果表明,经过22 a的耕作,5种耕作方式对紫色水稻土剖面Fe、Cu、Zn、Pb、Cd总量的剖面分布状况影响不显著,而对土壤Mn的剖面分布状况影响显著,常规平作、水旱轮作及免耕冬水均导致表层土壤Mn向下层淋失.5种耕作方式下土壤Fe、Cu、Zn、Pb和Cd的有效量均随土层深度的增加呈降低趋势,而常规平作、免耕冬水、垄作免耕及厢作免耕土壤Mn有效量则表现出随土层深度的增加而增高的趋势.5种耕作方式下,表层土壤Fe、Mn有效量以水旱轮作最高,Zn、Pb有效量以常规平作最高,而Cu有效量受耕作方式的影响不显著.相关分析结果表明,表层土壤有效Fe与pH呈极显著的负相关关系,与有机质呈显著的负相关关系,有效Mn与pH和有机质均呈极显著的负相关关系,有效Zn与总Zn呈显著正相关关系.水旱轮作、垄作免耕及厢作免耕条件下水稻根部Fe、Mn含量,茎叶Fe、Mn、Cu、Cd含量,糙米Cu含量均高于常规平作和免耕冬水,水旱轮作能明显降低Cd向糙米的迁移系数,对降低糙米Cd含量有明显的效果,且水旱轮作条件下糙米Cd含量低于国家食品卫生标准.水稻根部Fe含量与pH呈极显著负相关关系,与有效Fe呈极显著正相关关系,根部Mn含量与pH呈极显著负相关关系,与有效Mn呈极显著正相关关系,茎叶中Mn含量与pH呈显著的负相关关系,与总Mn及有效Mn呈显著的正相关关系,茎叶和糙米Cu含量与pH均呈极显著的负相关关系,糙米中Zn含量与pH呈显著负相关关系,与CEC呈极显著正相关关系.结果表明,耕作方式主要通过影响土壤pH而影响土壤重金属的有效量及水稻重金属的含量,水旱轮作可提高表层土壤Fe、Mn活性,降低土壤Zn、Pb和Cd活性,并能在一定程度上降低糙米Pb、Cd含量,但也应注意长期的水旱轮作可能会导致表层土壤Mn过度向下层淋溶.     

土壤调理剂对土壤-水稻系统Cd、Zn迁移累积的影响及健康风险评价

选取湖南省长沙市北山镇某中重度Cd污染稻田,研究了土壤调理剂(石灰石+偏高岭土+钙镁磷肥)对稻田土壤重金属Cd、Zn的钝化效果,以及对水稻各部位累积Cd和Zn的影响,并进行了Cd的健康风险评价.结果表明,使用土壤调理剂提高了稻田土壤p H值.Cd的CaCl_2提取态含量降低了0.9%~24.1%,Zn的CaCl_2提取态含量降低了22.5%~69.6%.土壤调理剂显著降低了水稻糙米中Cd与Zn的含量,与对照相比分别降低了10.8%~47.3%、10.3%~17.5%;土壤调理剂对水稻糙米Cd的吸收和累积的影响要远大于Zn,水稻糙米中的Cd/Zn比随着土壤调理剂施用量的增加而显著降低.研究区大米重金属Cd目标危害系数THQ值大于1,说明当地人群通过食用大米途径摄入重金属Cd存在健康风险.土壤调理剂有效地抑制了水稻植株对土壤中Cd的吸收,并降低了Cd/Zn比,使糙米中的Cd含量显著降低,从而降低了当地人群通过食用大米途径摄入重金属Cd的健康风险.     

钙镁磷肥对石灰、海泡石组配修复镉污染稻田土壤的影响

改良剂组配(例如羟基磷灰石和沸石)可有效降低土壤中重金属的生物有效性,抑制水稻对重金属的积累,从而提高农产品的安全水平.本文通过田间试验,研究钙镁磷肥施用对石灰、海泡石组配降低稻田土壤有效态Cd含量、水稻各部分中Cd含量的影响.结果表明,施用钙镁磷肥可显著促进石灰、海泡石组配的钝化修复效果.与石灰、海泡石组配处理相比,施用钙镁磷肥,土壤中有效态Cd含量和糙米中Cd含量显著降低,在施用2 250 kg·hm~(-2)钙镁磷肥的条件下,土壤中Cd~(2+)发生沉淀或络合反应生成难溶性磷酸镉而降低土壤酸可提取态、可还原态和可氧化态Cd的占比,土壤中有效态Cd含量显著(P0.05)降低46.97%,糙米中Cd含量降低至0.04 mg·kg~(-1),低于《食品安全国家标准》(GB 2762-2017)中糙米镉限量(0.2 mg·kg~(-1))标准,且糙米产量增加28.34%.相关性分析结果表明,水稻根、茎叶和糙米中Cd含量与土壤中有效态Cd含量,水稻糙米中Cd含量与根和茎叶中Cd含量呈极显著正相关关系(P0.01),土壤有效态Cd含量是影响水稻糙米中Cd含量的关键性因素,钙镁磷肥可提高石灰与海泡石对土壤中有效态Cd降低效果来减少水稻根和茎叶对Cd的吸收,进而降低糙米中Cd含量.上述结果表明,施用钙镁磷肥提高了石灰、海泡石组配降低糙米中Cd含量的效果,可实现Cd污染稻田水稻安全生产和增产.     

含磷物质对水稻吸收土壤砷的影响

向砷(As)污染土壤中施用磷酸氢二钠(DSP)和羟基磷灰石(HAP),通过水稻盆栽试验研究含磷物质对水稻吸收土壤砷的影响.结果表明,DSP和HAP都显著增加了土壤pH值和土壤有效磷含量(P<0.05),活化了土壤中的砷,且DSP提高砷在土壤迁移的能力要强于HAP.DSP和HAP均使水稻根中总砷、糙米总砷、糙米无机砷含量显著降低,但HAP显著增加了水稻茎叶总砷含量.DSP和HAP降低糙米中无机砷的效果比总砷略好,DSP降低糙米中总砷和无机砷的效果与HAP基本相当.分析表明,水稻各器官中砷含量受磷砷拮抗作用和土壤中砷生物有效性增加这2个因素的影响,且在本试验条件下磷砷的拮抗作用在水稻根、糙米这两个部位中有明显体现.较低添加量(小于等于0.12 g·kg-1)的DSP和HAP使水稻总生物量和糙米产量有所增加,但随着添加量的继续增加,2种含磷物质明显抑制了水稻生长,且HAP的抑制作用相对较轻.     

Distribution and ecological effect of mercury in Laogang landfill, Shanghai, China

Laogang landfill near Shanghai is the largest landfill in China, and receives about 10000 t of daily garbage per day, Samples of topsoil and plants were analyzed to evaluate mercury pollution from the landfill. For topsoil samples, there were significant correlations among total mercury （HgT）, combinative mercury （Hgc） and gaseous mercury （HgG）, and content of total organic carbon （TOC）, but, no significantly relationship was found between Hg content and filling time. Hg content changes in vertical profiles with time showed that the average Hgv of profiles 1992, 1996, and 2000 was similar, but their average HgG was quite different. HgT was significantly correlated with Hgc in profile 1992 and 2000, and Hgv was significantly correlated with Hg6 in profile 1996. HgG/Hgv ratio in profile samples decreased in the order of （HgG,/HgT）1992〉（HgG/HgT）1996〉〉（HgG/HgT）2000. A simple outline of Hg release in landfill could be drawn： with increasing of filling time, degradation undergoes different biodegradation, accordingly, gaseous mercury goes through small, more, and small proportion to total mercury. Distribution of Hg in plants was inhomogeneous, following the order of leaf〉root〉stem. The highest value of leaf may be associated with higher atmospheric Hg from landfill. Ligneous plants （e.g. Phyllostachys glanca, Prunus salicina and Ligustrum lucidum） are capable of enriching more Hg than herbaceous plants.     

EDTA-enhanced phytoremediation of lead contaminated soil by Bidens maximowicziana

Phytoremediation is a potential cleanup technology for the removal of heavy metals from contaminated soils.Bidens maximowicziana is a new Pb hyperaccumulator,which not only has remarkable tolerance to Pb but also extraordinary accumulation capacity for Pb.The maximum Pb concentration was 1509.3 mg/kg in roots and 2164.7 mg/kg in overground tissues.The Pb distribution order in the B. maximowicziana was:leaf>stem>root.The effect of amendments on phytoremediation was also studied.The mobility of soil Pb and the Pb concentrations in plants were both increased by EDTA application.Compared with CK(control check),EDTA application promoted translocation of Pb to overground parts of the plant.The Pb concentrations in overground parts of plants was increased from 24.23-680.56 mg/kg to 29.07-1905.57 mg/kg.This research demonstrated that B.maximowicziana appeared to be suitable for phytoremediation of Pb contaminated soil,especially,combination with EDTA.     

Decomposition of alachlor by ozonation and its mechanism

Decomposition and corresponding mechanism of alachlor, an endocrine disruptor in water by ozonation were investigated. Results showed that alachlor could not be completely mineralized by ozone alone. Many intermediates and final products were formed during the process, including aromatic compounds, aliphatic carboxylic acids, and inorganic ions. In evoluting these products, some of them with weak polarity were qualitatively identified by GC-MS. The information of inorganic ions suggested that the dechlorination was the first and the fastest step in the ozonation of alachlor.     

Enzymatic oxidation of aqueous pentachlorophenol

The influence of the nonionic surfactant Tween 80 on pentachlorophenol （PCP） oxidation catalyzed by horseradish peroxidase was studied. The surfactant was tested at concentrations below and above its critical micelle concentration （CMC）. Enhancement of PCP removal was observed at sub-CMCs. The presence of Tween 80 in the reaction mixture reduced enzyme inactivation which occurred through a combination of free radical attack and sorption by precipitated products. A simple first-order model was able to simulate time profiles for enzyme inactivation in the presence or absence of Tween 80. At supra-CMCs, the surfactant caused noticeable reductions in PCP removal, presumably through micelle partitioning of PCP which precluded the hydrophobic PCP molecule from interacting with the enzyme.     

基于综合水质标识指数和对应分析法的校园河道水质评价

以三峡大学的校园河道求索溪为研究对象,利用综合水质标识指数法确定求索溪水质类别,分析其水质时空变化规律,并利用对应分析法得出求索溪中不同监测点的主要污染因子.研究结果表明:求索溪整体的综合水质标识指数为7.423,整体水质为劣V类(地表水环境质量标准GB 3838-2002)且黑臭.从时间变化来看,求索溪4月份的水质最差,5月份次之,4、5月份所有监测点的水质都劣于V类且黑臭;8月份水质最好,水质为Ⅳ类;从空间分布来看,8个监测点综合水质标识指数均超过6.0,水质为劣V类,其中6号监测点的水质相对最好,监测点3号的水质相对最差;对应分析法得出求索溪的整体水体污染程度受总氮因子的影响最大,其次为总磷.该研究拟为求索溪及类似校园河道的水环境治理研究提供基础依据和参考.     

Effects of chitosan on growth of an aquatic plant (Hydrilla verticillata) in polluted waters with different chemical oxygen demands

Effects of chitosan on a submersed plant, Hydrilla verticillata, were investigated. Results indicated that H. venicillata could prevent ultrastructure phytotoxicities and oxidativereaction from polluted water with high chemical oxygen demand (COD). Superoxide dismutase (SOD) activity and malondialdehyde (MDA) contents in H. verticillata treated with 0.1% chitosan in wastewater increased with high COD (980 mg/L) and decreased with low COD (63 mg/L), respectively. Ultrastructural analysis showed that the stroma and grana of chloroplast basically remained normal. However, plant cells from the control experiment (untreated with chitosan) were vacuolated and the cell interval increased. The relict of protoplast moved to the center, with cells tending to disjoint. Our findings indicate that wastewater with high COD concentration can cause a substantial damage to submersed plant, nevertheless, chitosan probably could alleviate the membrane lipid peroxidization and ultrastructure phytotoxicities, and protect plant cells from stress of high COD concentration polluted water.     

Removal of cadmium using MnO2 loaded D301 resin

MnO2 loaded weak basic anion exchange resin D301 （Anion exchange resin, macroreticular weak basic styrene） as adsorbent has been prepared and applied to the removal of cadmium. The adsorption characteristics have been investigated with respect to effect of pH, equilibrium isotherms, removal kinetic data, and interference of the coexisting ions. The results indicated that the Cd^2＋ could be efficiently removed using MnO2 loaded D301 resin in the pH range of 3-8 from aqueous solutions with the co-existence of high concentration of alkali and alkaline-earth metals ions. The saturate adsorption capacity of the Cd^2＋ was 77.88 mg/g. The adsorption process followed the pseudo first-order kinetics. The equilibrium data obtained in this study accorded excellently with the Langmuir adsorption isotherm.     

Effect of coagulation pretreatment on the fouling of ultrafiltration membrane

The purpose of this study is to understand the effect and mechanism of preventing membrane fouling, by coagulation pretreatment, in terms of fractional component and molecular weight of natural organic matter （NOM）. A relatively higher molecular weight （MW） of hydrophobic compounds was responsible for a rapid decline in the ultrafiltration flux. Coagulation could effectively remove the hydrophobic organics, resulting in the increase of flux. It was found that a lower MW of neutral hydrophilic compounds, which could remove inadequately by coagulation, was responsible for the slow declining flux. The fluxes in the filtration of coagulated water and supernatant water were compared and the results showed that a lower MW of neutral hydrophilic compounds remained in the supernatant water after coagulation could be rejected by a membrane, resulting in fouling. It was also found that the coagulated flocs could absorb neutral hydrophilic compounds effectively. Therefore, with the coagulated flocs formed on the membrane surface, the flux decline could be improved.     

Penetration analysis of elements and bioleaching treatment of spent refractory for recycling

Acidithiobacillus ferrooxidans ATCC23270 and Acidithiobacillus thiooxidans TM-32 were used for bioleaching of spent refractories of aluminium and copper melting furnaces for their recycling.Firstly,penetration of elements into aluminium melting furnace refractory was investigated and it was found that up to 7 cm from surface was contaminated.Comparison on leaching efficiency by the strains ATCC23270 and TM-32 found that the strain ATCC23270 could treat larger amount of the refractories than the strain TM-32 could do.In the experiment of bioleaching of spent refractory aluminium melting furnace by the strain ATCC23270,high leaching efficiency were obtained on Al,Si,and Ca,and extremely low leaching performance was,however,shown on the rest of elements i.e.,Na,Mn,and Zn.Under the strain TM-32 use,relatively high leaching performance was recognized on Al,Si,Ca,Na,Mn,and Zn.In the experiment of bioleaching for spent refractory copper melting furnace,almost the same leaching trends were shown on Cu,Zn,Al,and Si under the strains ACTT23270 and TM-32 uses.     

Simultaneous removal of ammonium and phosphate by zeolite synthesized from coal fly ash as influenced by acid treatment

Zeolite synthesized from fly ash （ZFA） without modification is not efficient for the purification of NH4＋ and phosphate at low concentrations that occur in real effluents, despite the high potential removal capacity. To develop an effective technique to enhance the removal efficiency of ammonium and phosphate at low concentrations, ZFA was modified with acid treatment and the simultaneous removal of ammonium and phosphate in a wide range of concentration was investigated. It was seen that when compared with untreated ZFA, only the treatment by 0.01 mol/L of H2SO4 significantly improved the removal efficiency of ammonium at low initial concentrations. The behavior was well explained by the pH effect. Treatment by more concentrated H2SO4 led to the deterioration of the ZFA structure and a decrease in the cation exchange capacity. Treatment by 0.01 mol/L H2SO4 improved the removal efficiency of phosphate by ZFA at all initial P concentrations, while the treatment by concentrated H2SO4 （≥0.9 mol/L） resulted in a limited maximum phosphate immobilization capacity （PIC）. It was concluded that through a previous mild acid treatment （e.g. 0.01 mol/L of H2SO4）, ZFA can be used in the simultaneous removal of NH4＋ and P at low concentrations simulating real effluent.